Ester compound and use thereof

ABSTRACT

An ester compound represented by formula (1): 
                         
wherein R 1  represents C 1 -C 4  alkyl, has an excellent pest control effect and is therefore useful as an active ingredient of a pest control agent.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a National Stage of International Application No.PCT/JP2011/054220 filed Feb. 18, 2011, claiming priority based onJapanese Patent Application No. 2010-039981 filed Feb. 25, 2010, thecontents of all of which are incorporated herein by reference in theirentirety.

TECHNICAL FIELD

The present invention relates to an ester compound and use thereof.

BACKGROUND ART

Heretofore, various compounds have been synthesized so as to controlpests. For example, a certain ester compound is described inJP-A-60-16962 and JP-A-57-158765.

DISCLOSURE OF INVENTION

An object of the present invention is to provide a novel compound havingan excellent pest control effect.

The present inventors have intensively studied and found that an estercompound represented by formula (1) shown below has an excellent pestcontrol effect, and led to the present invention.

That is, the present invention is directed to the following invention:

[1] An ester compound represented by formula (1):

wherein R¹ represents C₁-C₄ alkyl,(hereinafter referred to as the compound of the present invention);[2] The ester compound according to [1], wherein a relativeconfiguration of the substituent at the 1-position of the cyclopropanering and the substituent at the 3-position of the cyclopropane ring is atrans configuration in formula (1);[3] The ester compound according to [1], wherein an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration in formula (1);[4] The ester compound according to [1], wherein an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration, and a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration in formula(1);[5] The ester compound according to any one of [1] to [4], wherein adouble bond of the substituent at the 3-position of the cyclopropanering is in the E configuration or a mixture of E configuration and Zconfiguration, and the proportion of the E configuration is 50% or morein formula (1);[6] The ester compound according to any one of [1] to [4], a double bondof the substituent at the 3-position of the cyclopropane ring is in theE configuration in formula (1);[7] The ester compound according to any one of [1] to [4], wherein R¹ ismethyl in formula (1);[8] The ester compound according to any one of [1] to [4], wherein R¹ isethyl in formula (1);[9] The ester compound according to [5], wherein R¹ is methyl in formula(1);[10] The ester compound according to [5], wherein R¹ is ethyl in formula(1);[11] The ester compound according to [6], wherein R¹ is methyl informula (1);[12] The ester compound according to [6], wherein R¹ is ethyl in formula(1);[13] A pest control agent comprising the ester compound according to anyone of [1] to [12] and an inert carrier;[14] A method of controlling pests, which comprises a step of applyingan effective amount of the ester compound according to any one of [1] to[12] to pests or a place where pests habitat;[15] A method of controlling pests, which comprises the step of applyingan effective amount of the ester compound according to any one of [1] to[12] to cockroaches or a place where cockroaches inhabits;[16] The method of controlling pests according to [15], wherein thecockroach is American cockroach (Periplaneta Americana);[17] The method of controlling pests according to [15], wherein thecockroach is German cockroach (Blattella germanica);[18] A method of controlling pests, which comprises a step of sprayingan effective amount of the ester compound according to any one of [1] to[12] to cockroaches or a place where cockroaches inhabit;[19] The method of controlling pests according to [18], wherein thecockroach is American cockroach (Periplaneta Americana);[20] The method of controlling pests according to [18], wherein thecockroach is German cockroach (Blattella germanica).

The compound of the present invention has an excellent pest controleffect and is therefore useful as an active ingredient of a pest controlagent.

In the compound of the present invention, there are isomers derived fromtwo asymmetric carbon atoms at the 1-position and the 3-position on thecyclopropane ring, and isomers derived from the double bond present inthe substituent at the 3-position of the cyclopropane ring. Each isomerhaving pest control activity or a mixture of those isomers in anarbitrary ratio which has pest control activity are included in thepresent invention.

Examples of the C₁-C₄ alkyl represented by R¹ include methyl, ethyl,propyl, butyl and isopropyl.

Examples of the compound of the present invention include the followingcompounds.

A compound represented by formula (1) in which a relative configurationof the substituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration;

A compound represented by formula (1) in which the absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration;

A compound represented by formula (1) in which an absolute configurationof the 1-position of the cyclopropane ring is an R configuration, and arelative configuration of the substituent at the 1-position of thecyclopropane ring and the substituent at the 3-position of thecyclopropane ring is a trans configuration;A compound represented by formula (1) in which the double bond of thesubstituent at the 3-position of the cyclopropane ring is in the Econfiguration or a mixture of E configuration and Z configuration, andthe proportion of the E configuration is 50% or more;A compound represented by formula (1) in which a relative configurationof the substituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration, the double bond of the substituent at the 3-position ofthe cyclopropane ring is in the E configuration or a mixture of Econfiguration and Z configuration, and the proportion of the Econfiguration is 50% or more;A compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, thedouble bond of the substituent at the 3-position of the cyclopropanering is in the E configuration or a mixture of E configuration and Zconfiguration, and the proportion of the E configuration is 50% or more;A compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, arelative configuration of the substituent at the 1-position of thecyclopropane ring and the substituent at the 3-position of thecyclopropane ring is a trans configuration, the double bond of thesubstituent at the 3-position of the cyclopropane ring is in the Econfiguration or a mixture of E configuration and Z configuration, andthe proportion of the E configuration is 50% or more;A compound represented by formula (1) in which the double bond of thesubstituent at the 3-position of the cyclopropane ring is in the Econfiguration.A compound represented by formula (1) in which a relative configurationof the substituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration, and the double bond of the substituent at the 3-positionof the cyclopropane ring is in the E configuration.A compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, and thedouble bond of the substituent at the 3-position of the cyclopropanering is in the E configuration.A compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, arelative configuration of the substituent at the 1-position of thecyclopropane ring and the substituent at the 3-position of thecyclopropane ring is a trans configuration, and the double bond of thesubstituent at the 3-position of the cyclopropane ring is in the Econfiguration.A compound represented by formula (1) in which a relative configurationof the substituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration, and R¹ is methyl;A compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, and R¹ ismethyl;A compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, arelative configuration of the substituent at the 1-position of thecyclopropane ring and the substituent at the 3-position of thecyclopropane ring is a trans configuration, and R¹ is methyl;A compound represented by formula (1) in which the double bond of thesubstituent at the 3-position of the cyclopropane ring is in the Econfiguration or a mixture of E configuration and Z configuration, theproportion of the E configuration is 50% or more, and R¹ is methyl;A compound represented by formula (1) in which a relative configurationof the substituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration, the double bond of the substituent at the 3-position ofthe cyclopropane ring is in the E configuration or a mixture of Econfiguration and Z configuration, the proportion of the E configurationis 50% or more, and R¹ is methyl;A compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, thedouble bond of the substituent at the 3-position of the cyclopropanering is in the E configuration or a mixture of E configuration and Zconfiguration, the proportion of the E configuration is 50% or more, andR¹ is methyl;A compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, arelative configuration of the substituent at the 1-position of thecyclopropane ring and the substituent at the 3-position of thecyclopropane ring is a trans configuration, the double bond of thesubstituent at the 3-position of the cyclopropane ring is in the Econfiguration or a mixture of E configuration and Z configuration, theproportion of the E configuration is 50% or more, and R¹ is methyl;A compound represented by formula (1) in which the double bond of thesubstituent at the 3-position of the cyclopropane ring is in the Econfiguration, and R¹ is methyl.A compound represented by formula (1) in which a relative configurationof the substituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration, the double bond of the substituent at the 3-position ofthe cyclopropane ring is in the E configuration, and R¹ is methyl.A compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, thedouble bond of the substituent at the 3-position of the cyclopropanering is in the E configuration, and R¹ is methyl.A compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, arelative configuration of the substituent at the 1-position of thecyclopropane ring and the substituent at the 3-position of thecyclopropane ring is a trans configuration, the double bond of thesubstituent at the 3-position of the cyclopropane ring is in the Econfiguration, and R¹ is methyl.A compound represented by formula (1) in which a relative configurationof the substituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration, and R¹ is ethyl;A compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, and R¹ isethyl;A compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, arelative configuration of the substituent at the 1-position of thecyclopropane ring and the substituent at the 3-position of thecyclopropane ring is a trans configuration, and R¹ is ethyl;A compound represented by formula (1) in which the double bond of thesubstituent at the 3-position of the cyclopropane ring is in the Econfiguration or a mixture of E configuration and Z configuration, theproportion of the E configuration is 50% or more, and R¹ is ethyl;A compound represented by formula (1) in which a relative configurationof the substituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration, the double bond of the substituent at the 3-position ofthe cyclopropane ring is in the E configuration or a mixture of Econfiguration and Z configuration, the proportion of the E configurationis 50% or more, and R¹ is ethyl;A compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, thedouble bond of the substituent at the 3-position of the cyclopropanering is in the E configuration or a mixture of E configuration and Zconfiguration, the proportion of the E configuration is 50% or more, andR¹ is ethyl;A compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, arelative configuration of the substituent at the 1-position of thecyclopropane ring and the substituent at the 3-position of thecyclopropane ring is a trans configuration, the double bond of thesubstituent at the 3-position of the cyclopropane ring is in the Econfiguration or a mixture of E configuration and Z configuration, theproportion of the E configuration is 50% or more, and R¹ is ethyl;A compound represented by formula (1) in which the double bond of thesubstituent at the 3-position of the cyclopropane ring is in the Econfiguration, and R¹ is ethyl.A compound represented by formula (1) in which a relative configurationof the substituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration, the double bond of the substituent at the 3-position ofthe cyclopropane ring is in the E configuration, and R¹ is ethyl.A compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, thedouble bond of the substituent at the 3-position of the cyclopropanering is in the E configuration, and R¹ is ethyl.A compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, arelative configuration of the substituent at the 1-position of thecyclopropane ring and the substituent at the 3-position of thecyclopropane ring is a trans configuration, the double bond of thesubstituent at the 3-position of the cyclopropane ring is in the Econfiguration, and R¹ is ethyl.A compound represented by formula (1) in which a relative configurationof the substituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a cisconfiguration;A compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, and arelative configuration of the substituent at the 1-position of thecyclopropane ring and the substituent at the 3-position of thecyclopropane ring is a cis configuration;A compound represented by formula (1) in which a relative configurationof the substituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a cisconfiguration, and the double bond of the substituent at the 3-positionof the cyclopropane ring is in the E configuration; andA compound represented by formula (1) in which absolute configuration ofthe 1-position of the cyclopropane ring is an R configuration, arelative configuration of the substituent at the 1-position of thecyclopropane ring and the substituent at the 3-position of thecyclopropane ring is a cis configuration, and the double bond of thesubstituent at the 3-position of the cyclopropane ring is in the Econfiguration.

The method for producing the compound of the present invention will bedescribed below.

The compound of the present invention can be produced, for example, bythe following process.

(Production Process 1)

A process of reacting an alcohol compound represented by formula (2):

with a carboxylic acid compound represented by formula (3):

wherein R¹ represents the same meanings as described above, or areactive derivative thereof.

Examples of the reactive derivative include an acid halide of thecarboxylic acid compound represented by formula (3), an acid anhydrideof the carboxylic acid compound represented by formula (3), an ester ofthe carboxylic acid compound represented by formula (3) and so on.Examples of the acid halide include an acid chloride compound and anacid bromide compound, and examples of the ester include a methyl ester,an ethyl ester and so on.

The reaction is usually conducted in a solvent in the presence of acondensing agent or a base.

Examples of the condensing agent used in the reaction includedicyclohexylcarbodiimide and1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride.

Examples of the base used in the reaction include organic bases such astriethylamine, pyridine, N,N-diethylaniline, 4-dimethylaminopyridine anddiisopropylethylamine.

Examples of the solvent used in the reaction hydrocarbons such asbenzene, toluene and hexane; ethers such as diethylether andtetrahydrofuran; halogenated hydrocarbons such as chloroform,dichloromethane, 1,2-dichloroethane and chlorobenzene; a mixture ofthese solvents; and so on.

The reaction time of the reaction is usually within a range from 5minutes to 72 hours.

The reaction temperature of the reaction is usually within a range from−20° C. to 100° C. (from −20° C. to a boiling point of a solvent in casethe boiling point of the solvent to be used is lower than 100° C.), andpreferably from −5° C. to 100° C. (from −5° C. to a boiling point of asolvent in case the boiling point of the solvent to be used is lowerthan 100° C.).

In the reaction, a molar ratio of the alcohol compound represented byformula (2) to the carboxylic acid compound represented by formula (3)or a reactive derivative thereof to be used can be arbitrarily set, andpreferably an equimolar ratio or a ratio close thereto.

The condensing agent or base can be usually used in an arbitraryproportion within a range from 0.25 mol to an excessive amount, andpreferably from 1.0 mol to 2 mol, based on 1 mol of the alcohol compoundrepresented by formula (2). These condensing agents or bases areappropriately selected according to the kind of the carboxylic acidcompound represented by formula (3) or a reactive derivative thereof.

After the completion of the reaction, the reaction mixture is usuallysubjected to be worked up, for example, the reaction mixture is filteredand then the filtrate is concentrated, or the reaction mixture is pouredinto water and the resulting solution is extracted with an organicsolvent and then concentrated, and thus the compound of the presentinvention can be obtained. The obtained compound of the presentinvention can be purified by an operation such as chromatography.

(Production Process 2)

Among the compound of the present invention, a compound represented byformula (1-1) in which a relative configuration of the substituent atthe 1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a cis configuration can beproduced by the process shown below.

Formula (1-1)

wherein R¹ represents the same meanings as described above. A process ofreacting a lactone compound represented by formula (4):

wherein R¹ represents the same meanings as described above, with acompound represented by formula (5)

in the presence of a base.

The reaction is usually conducted in a solvent in the presence of abase. Examples of the solvent used in the reaction include ketones suchas acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers suchas tetrahydrofuran; halogenated hydrocarbons such as chloroform,dichloromethane, 1,2-dichloroethane and chlorobenzene; acid amides suchas N,N-dimethylformamide; sulfoxides such as dimethyl sulfoxide; amixture of these solvents; and so on.

Examples of the base used in the reaction include carbonates such assodium carbonate, potassium carbonate and cesium carbonate.

The reaction time of the reaction is usually within a range from 5minutes to 72 hours.

The reaction temperature of the reaction is usually within a range from−20° C. to 100° C. (from −20° C. to a boiling point of a solvent in casethe boiling point of the solvent to be used is lower than 100° C.), andpreferably from −5° C. to 100° C. (from −5° C. to a boiling point of asolvent in case the boiling point of the solvent to be used is lowerthan 100° C.).

In the reaction, a molar ratio of the lactone compound represented byformula (4) to the compound represented by formula (5) to be used can bearbitrarily set, and preferably an equimolar ratio or a ratio closethereto.

The base can be usually used in an arbitrary proportion within a rangefrom 0.25 mol to an excessive amount, and preferably from 0.5 mol to 2mol, based on 1 mol of the lactone compound represented by formula (4).

After the completion of the reaction, the reaction mixture is usuallysubjected to be worked up, for example, the reaction mixture is filteredand then the filtrate is concentrated, or the reaction mixture is pouredinto water and the resulting solution is extracted with an organicsolvent and then concentrated, and thus the compound represented byformula (1-1) can be isolated. The compound represented by formula (1-1)can be purified by an operation such as chromatography.

An alcohol compound represented by formula (2) is a compound describedin JP-A-57-158765.

An intermediate of the present invention can be produced, for example,by the process shown below.

(Reference Production Process 1)

Among the carboxylic acid compound represented by formula (3), acarboxylic acid compound represented by formula (3-1) in which arelative configuration of the substituent at the 1-position of thecyclopropane ring and the substituent at the 3-position of thecyclopropane ring is a trans configuration can be produced, for example,by the process shown below.

(First Step)

A caronaldehyde ester derivative represented by formula (6):

wherein R² represents C₁-C₅ alkyl, is reacted with a nitrile compoundrepresented by formula (7):

wherein R¹ represents the same meanings as described above, in thepresence of a base, and thus a compound represented by formula (8):

wherein R¹ and R² represents the same meanings as described above, canbe produced.(Second Step)

The compound represented by formula (8) is subjected to a hydrolysisreaction in the presence of a base, and thus a carboxylic acid compoundrepresented by formula (3-1):

wherein R¹ represents the same meanings as described above, can beproduced.

The reaction of the first step is usually conducted by using the nitrilecompound represented by formula (7) in the proportion of 1.0 to 1.5 moland a base in the proportion of 1 to 10 mol, based on 1 mol of thecaronaldehyde ester derivative represented by formula (6), and reactingthem in a polar solvent at 0° C. to 80° C., and preferably 0° C. to 30°C. Examples of the based used in the reaction include carbonates such aspotassium carbonate and sodium carbonate; and alkali metal compoundssuch as sodium hydride. Examples of the polar solvent used in thereaction include acid amides such as N,N-dimethylformamide; andsulfoxides such as dimethyl sulfoxide.

After the completion of the reaction, the reaction mixture is usuallysubjected to be worked up, for example, the reaction mixture is added towater and the resulting solution is extracted with an organic solvent,and then the organic layer is dried and concentrated, and thus thecompound represented by formula (8) can be obtained.

The reaction of the second step is usually conducted by using a base inthe proportion of 1 to 10 mol based on 1 mol of the compound representedby formula (8) in a solvent at 0° C. to 80° C., and preferably 0° C. to30° C. Examples of the base used in the reaction include hydroxides suchas potassium hydroxide and sodium hydroxide. Examples of the solventused in the reaction usually a mixture of water and ethers such astetrahydrofuran or a mixture of water and alcohols such as methanol.

After the completion of the reaction, the reaction mixture is subjectedto be worked up, for example, the reaction mixture is acidified and thenextracted with an organic solvent, and then the organic layer is driedand concentrated, and thus the carboxylic acid compound represented byformula (3-1) can be obtained.

The caronaldehyde ester derivative represented by formula (6) is acompound described in Tetrahedron 45, 3039-3052 (1989).

(Reference Production Process 2)

A lactone compound represented by formula (4):

wherein R¹ represents the same meanings as described above, can beproduced, for example, by reacting a lactol derivative represented byformula (9):

with a nitrile compound represented by formula (7):

wherein R¹ represents the same meanings as described above, in thepresence of a base.

The reaction is usually conducted by using the nitrile compoundrepresented by formula (7) in the proportion of 1.0 to 1.5 mol and thebase in the proportion of 1 to 10 mol, based on 1 mol of the lactolderivative represented by formula (9) in a polar solvent at 0° C. to 80°C., and preferably 0° C. to 50° C. Examples of the based used in thereaction include carbonates such as potassium carbonate and sodiumcarbonate; and alkali metal compounds such as sodium hydride. Examplesof the polar solvent used in the reaction include the reaction includeacid amides such as N,N-dimethylformamide; and sulfoxides such asdimethyl sulfoxide.

After the completion of the reaction, the reaction mixture is subjectedto be worked up, for example, the reaction mixture is acidified andextracted with an organic solvent, and then the organic layer is driedand concentrated, and thus the lactone compound represented by formula(4) can be isolated.

The lactol derivative represented by formula (9) is a compound describedin Synthetic Communications, 17, 1089-1094 (1987).

Examples of pests on which the compound of the present invention has acontrol effect include harmful arthropod pests such as harmful insectsand harmful acarines, and more specifically, the following pests.

Hemiptera: planthoppers such as Laodelphax striatellus, Nilaparvatalugens, and Sogatella furcifera, leafhoppers such as Nephotettixcincticeps, and Nephotettix virescens, aphids such as Aphis gossypii,and Myzus persicae, plant bugs such as Nezara antennata, Riptortusclavetus, Eysarcoris lewisi, Eysarcoris parvus, Plautia stali, andHalyomorpha mista, white flies such as Trialeurodes vaporariorum,Bemisia tabaci, and Bemisia argentifolii, scales such as Aonidiellaaurantii, Comstockaspis perniciosa, Unaspis citri, Ceroplastes rubens,and Icerya purchasi, lace bugs, bed bugs such as Cimex lectularius,jumping plantlice and so on;

Lepidoptera: Pyralidae such as Chilo suppressalis, Cnaphalocrocismedinalis, Notarcha derogata, and Plodia interpunctella, Spodopteralitura, Pseudaletia separata, Noctuidae such as Trichoplusia spp.,Heliothis spp., and Earias spp., Pieridae such as Pieris rapae,Tortricidae such as Adoxopheys spp., Grapholita molesta, Adoxophyesorana fasciata, and Cydia pomonella, Carposinidae such as Carposinaniponensis, Lyonetiidae such as Lyonetia spp., Lymantriidae such asLymantria spp., Lymantriidae such as Euproctis spp., Yponameutidae suchas Plutella xylostella, Gelechiidae such as Pectinophora gossypiella,Arctiidae such as Hyphantria cunea, Tineidae such as Tinea translucens,and Tineola bisselliella, and so on;

Diptera: Culex spp. such as Culex pipiens pallens, Culextritaeniorhynchus, and Culex quinquefasciatus, Aedes spp. such as Aedesaegypti, and Aedes albopictus, Anopheles spp. such as Anophelessinensis, and Anopheles gambiae, Chironomidae, Muscidae such as Muscadomestica, and Muscina stabulans, Calliphoridae, Sarcophagidae, littlehousefly, Anthomyiidae such as Delia platura, and Delia antiqua,Tephritidae, Drosophilidae, Phoridae such as Megaselia spiracularis,Clogmia albipunctata, Psychodidae, Simuliidae, Tabanidae, Stomoxyidae,Agromyzidae, and so on;

Coleoptera: Diabrotica spp. such as Diabrotica virgifera virgifera, andDiabrotica undecimpunctata howardi, Scarabaeidae such as Anomala cuprea,and Anomala rufocuprea, Curculionidae such as Sitophilus zeamais,Lissorhoptrus oryzophilus, and Callosobruchuys chienensis, Tenebrionidaesuch as Tenebrio molitor, and Tribolium castaneum, Chrysomelidae such asOulema oryzae, Aulacophora femoralis, Phyllotreta striolata, andLeptinotarsa decemlineata, Dermestidae such as Dermestes maculates,Anobiidae, Epilachna spp. such as Epilachna vigintioctopunctata,Lyctidae, Bostrychidae, Ptinidae, Cerambycidae, Paederus fuscipes, andso on;

Blattodea: Blattella germanica, Periplaneta fuliginosa, Periplanetaamericana, Periplaneta brunnea, Blatta orientalis, and so on;

Thysanoptera: Thrips palmi, Thrips tabaci, Frankliniella occidentalis,Frankliniella intonsa, and so on;

Hymenoptera: Formicidae such as Monomorium pharaosis, Formica fuscajaponica, Ochetellus glaber, Pristomyrmex pungens, Pheidole noda, andLinepithema humile, long-legged wasps such as Polistes chinensisantennalis, Polistes jadwigae, and Polistes rothneyi, Vespidae such asVespa mandarinia japonica, Vespa simillima, Vespa analis insularis,Vespa crabro flavofasciata, and Vespa ducalis, Bethylidae, Xylocopa,Pompilidae, Sphecoidae, mason wasp, and so on;

Orthoptera: mole crickets, grasshoppers, etc.;

Shiphonaptera: Ctenocephalides felis, Ctenocephalides canis, Pulexirritans, Xenopsylla cheopis, and so on;

Anoplura: Pediculus humanus corporis, Phthirus pubis, Haematopinuseurysternus, Dalmalinia ovis, and so on;

Isoptera: Reticulitermes spp. such as Reticulitermes speratus,Coptotermes formosanus, Reticulitermes flavipes, Reticulitermeshesperus, Reticulitermes virginicus, Reticulitermes tibialis, andHeterotermes aureus, Incisitermes spp. such as Incisitermes minor, andZootermopsis spp. such as Zootermopsis nevadensis, and so on;

Acarina: Tetranychidae such as Tetranychus urticae, Tetranychuskanzawai, Panonychus citri, Panonychus ulmi, and Oligonychus spp.,Eriophyidae such as Aculops pelekassi, and Aculus schlechtendali,Tarsonemidae such as Polyphagotarsonemus latus, Tenuipalpidae,Tuckerellidae, Ixodidae such as Haemaphysalis longicornis, Haemaphysalisflava, Dermacentor variabilis, Ixodes ovatus, Ixodes persulcatus),Ixodes scapularis, Boophilus microplus, Amblyomma americanum, andRhipicephalus sanguineus, Acaridae such as Tyrophagus putrescentiae,Dermanyssidae such as Dermatophagoides farinae, Dermatophagoidesptrenyssnus, Cheyletidae such as Cheyletus eruditus, Cheyletusmalaccensis, and Cheyletus moorei, chicken mite such as Ornithonyssusbacoti, Ornithonyssus sylvairum, and Dermanyssus gallinae, Trombiculidaesuch as Leptotrombidium akamushi, and so on;

Araneae: Japanese foliage spider (Chiracanthium japonicum), redbackspider (Latrodectus hasseltii), Nephila clavata (Tetragnathidae),Cyclosa octotuberculata, St. Andrew's cross spider (Argiope amoena),Wasp sopider (Argiope bruennichii), orb-weaving spider (Araneusventricosus), grass spider (Agelena silvatica), wolf spider (Pardosaastrigera), dock spider (Dolomedes sulfurous), Carrhotus xanthogramma,common house spider (Achaearanea tepidariorum), Coelotes insidiosus,jumping spider (Salticidae), huntsman spider (Heteropoda venatoria),etc.;

Chilopoda: centipedes such as house centipede (Thereuonema hilgendorfi),Scolopendra subspinipes, Scolopendra subspinipes japonica,Scolopocryptops rubiginosus, Bothropolys asperatus, etc.;

Diplopoda: millipedes such as garden millipede (Oxidus gracilis), gardenmillipede (Nedyopus tambanus), train millipede (Parafontaria laminate),train millipede (Parafontaria laminata armigera), Parafontariaacutidens, Epanerchodus orientalis, etc.;

Isopoda: sow bugs such as Porcellionides pruinosus (Brandt), Porcellioscaber Latreille, pill bugs such as common pill bug (Armadillidiumvulgare), sea louses such as wharf roach (Ligia exotica), etc.;

Gastropoda: tree slug (Limax marginatus), yellow slug (Limax flavus),etc.

The pest control agent of the present invention contains the compound ofthe present invention and an inert carrier. The pest control agent ofthe present invention is usually formed into formulations describedbelow. Examples of the formulation include an oil solution, anemulsifiable concentrate, a wettable powder, a flowable formulation(e.g., an aqueous suspension, or an aqueous emulsion), a microcapsule, adust, a granule, a tablet, an aerosol, a carbon dioxide formulation, aheat transpiration formulation (e.g., an insecticidal coil, an electricinsecticidal mat, or a liquid absorbing core-type heat transpirationpesticide), a piezo insecticidal formulation, a heat fumigant (e.g., aself combustion-type fumigant, a chemical reaction-type fumigant, or aporous ceramic plate fumigant), an unheated transpiration formulation(e.g., a resin transpiration formulation, a paper transpirationformulation, an unwoven fabric transpiration formulation, a knit fabrictranspiration formulation, or a sublimating tablet), an aerosolformulation (e.g., a fogging formulation), a direct contact formulation(e.g., a sheet-shaped contact formulation, a tape-shaped contactformulation, or a net-shaped contact formulation), an ULV formulationand a poison bait

Examples of the method for formulation include the following methods.

(1) A method comprising mixing the compound of the present inventionwith a solid carrier, a liquid carrier, a gaseous carrier or a poisonbait, followed by addition of a surfactant and other auxiliary agentsfor formulation, and if necessary, further processing.(2) A method comprising impregnation of a base material containing noactive ingredient with the compound of the present invention.(3) A method comprising mixing the compound of the present invention anda base material, followed by subjecting the mixture to mold processing.

These formulations usually contain 0.001 to 98% by weight of thecompound of the present invention, depending on formulation forms.

Examples of the solid carrier used in the formulation include finepowders or granules of clays (e.g., kaolin clay, diatomaceous earth,bentonite, Fubasami clay, or acid white clay), synthetic hydratedsilicon oxide, talc, ceramics, other inorganic minerals (e.g., sericite,quartz, sulfur, active carbon, calcium carbonate, or hydrated silica)and fine powder and granulated substances such as chemical fertilizers(e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ammoniumchloride, or urea); substances that are solid at room temperature (e.g.,2,4,6-triisopropyl-1,3,5-trioxane, naphthalene, p-dichlorobenzene, orcamphor, adamantine); as well as felt, fiber, fabric, knit, sheet,paper, thread, foam, porous material and multi-filament comprising oneor more substances selected from the group consisting of wool, silk,cotton, hemp, pulp, synthetic resins (e.g., polyethylene resins such aslow density polyethylene, straight chain low density polyethylene andhigh density polyethylene; ethylene-vinyl ester copolymers such as anethylene-vinyl acetate copolymer; ethylene-methacrylate copolymers suchas an ethylene-methyl methacrylate copolymer and an ethylene-ethylmethacrylate copolymer; ethylene-acrylate copolymers such as anethylene-methyl acrylate copolymer and an ethylene-ethyl acrylatecopolymer; ethylene-vinylcarboxylic acid copolymers such as anethylene-acrylic acid copolymer; ethylene-tetracyclododecene copolymers;polypropylene resins such as a propylene homopolymer and apropylene-ethylene copolymer; poly-4-methylpentene-1, polybutene-1,polybutadiene, polystyrene; acrylonitrile-styrene resin;acrylonitrile-butadiene-styrene resins; styrene elastomers such as astyrene-conjugated diene block copolymer and a hydrogenatedstyrene-conjugated diene block copolymer; fluorine resins; acrylicresins such as methyl polymethacrylate; polyamide resins such as nylon 6and nylon 66; polyester resins such as polyethylene terephthalate,polyethylene naphthalate, polybutylene terephthalate andpolycyclohexylene dimethylene terephthalate; or porous resins such aspolycarbonate, polyacetal, polyacryl sulfone, polyarylate,hydroxybenzoic acid polyester, polyetherimide, polyester carbonate,polyphenylene ether resins, polyvinyl chloride, polyvinylidene chloride,polyurethane, foamed polyurethane, foamed polypropylene and foamedethylene), glass, metal and ceramics.

Examples of the liquid carrier include aromatic or aliphatichydrocarbons (e.g., xylene, toluene, alkylnaphthalene,phenylxylylethane, kerosene, light oil, hexane, or cyclohexane),halogenated hydrocarbons (e.g., chlorobenzene, dichloromethane,dichloroethane, or trichloroethane), alcohols (e.g., methanol, ethanol,isopropyl alcohol, butanol, hexanol, benzyl alcohol, or ethyleneglycol), ethers (e.g., diethyl ether, ethylene glycol dimethyl ether,diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,propylene glycol monomethyl ether, tetrahydrofuran, or dioxane), esters(e.g., ethyl acetate, or butyl acetate), ketones (e.g., acetone, methylethyl ketone, methyl isobutyl ketone, or cyclohexanone), nitriles (e.g.,acetonitrile, or isobutyronitrile), sulfoxides (e.g., dimethylsulfoxide), acid amides (e.g., N,N-dimethylformamide,N,N-dimethylacetamide, or N-methyl-pyrrolidone), alkylidene carbonate(e.g., propylene carbonate), vegetable oils (e.g., soybean oil, orcottonseed oil), plant essential oils (e.g., orange oil, hyssop oil, orlemon oil), and water.

Examples of the gaseous carrier include butane gas, chlorofluorocarbon,liquefied petroleum gas (LPG), dimethyl ether and carbon dioxide.

Examples of the surfactant include alkyl sulfate, alkyl sulfonate,alkylaryl sulfonate, alkylaryl ethers, polyoxyethylenated alkylarylethers, polyethylene glycol ethers, polyhydric alcohol esters and sugaralcohol derivatives.

Examples of the other auxiliary agents for formulation include a binder,a dispersant and a stabilizer. Specifically, there are, for example,casein, gelatin, polysaccharides (e.g., starch, gum arabic, cellulosederivatives, or alginic acid), lignin derivatives, bentonite,saccharides, synthetic water-soluble polymers (e.g., polyvinyl alcohol,or polyvinyl pyrrolidone), polyacrylic acid, BHT(2,6-di-tert-butyl-4-methylphenol) and BHA (a mixture of2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol).

Examples of a base material for the insecticidal coil include a mixtureof vegetable powder such as wood flour and lees powder, and a bindersuch as incense material powder, starch and gluten.

Examples of a base material for the electric insecticidal mat include aplate obtained by hardening cotton linter and a plate obtained byhardening fibrils of a mixture of cotton linter and pulp.

Examples of a base material for the self combustion-type fumigantinclude combustible exothermic agents such as nitrate, nitrite,guanidine salt, potassium chlorate, nitrocellulose, ethylcellulose andwood flour, thermal decomposition stimulants such as alkali metal salt,alkaline earth metal salt, dichromate and chromate, oxygen carriers suchas potassium nitrate, combustion-supporting agents such as melamine andflour starch, extenders such as diatomaceous earth, and binders such assynthetic glue.

Examples of a base material for the chemical reaction-type fumigantinclude exothermic agents such as alkali metal sulfide, polysulfide,hydrosulfide and calcium oxide, catalytic agents such as a carbonaceousmaterial, iron carbide and active white clay, organic foaming agentssuch as azodicarbonamide, benzenesulfonylhydrazide,dinitropentamethylenetetramine, polystyrene and polyurethane, andfillers such as strips of natural fiber and synthetic fiber.

Examples of a resin used as a base material of the resin transpirationformulation include polyethylene resins such as low densitypolyethylene, straight chain low density polyethylene and high densitypolyethylene; ethylene-vinyl ester copolymers such as an ethylene-vinylacetate copolymer; ethylene-methacrylate copolymers such as anethylene-methyl methacrylate copolymer and an ethylene-ethylmethacrylate copolymer; ethylene-acrylate copolymers such as anethylene-methyl acrylate copolymer and an ethylene-ethyl acrylatecopolymer; ethylene-vinylcarboxylic acid copolymers such as anethylene-acrylic acid copolymer; ethylene-tetracyclododecene copolymers;polypropylene resins such as a propylene copolymer and apropylene-ethylene copolymer; poly-4-methylpentene-1, polybutene-1,polybutadiene, polystyrene, acrylonitrile-styrene resins;acrylonitrile-butadiene-styrene resins; styrene elastomers such as astyrene-conjugated diene block copolymer and a hydrogenatedstyrene-conjugated diene block copolymer; fluorine resins; acrylicresins such as methyl polymethacrylate; polyamide resins such as nylon 6and nylon 66; polyester resins such as polyethylene terephthalate,polyethylene naphthalate, polybutylene butalate and polycyclohexylenedimethylene terephthalate; polycarbonate, polyacetal, polyacryl sulfone,polyarylate, hydroxybenzoic acid polyester, polyetherimide, polyestercarbonate, polyphenylene ether resin, polyvinyl chloride, polyvinylidenechloride and polyurethane. These base materials may be used alone or asa combination of two or more kinds. If necessary, a plasticizer such asphthalate esters (e.g., dimethyl phthalate, dioctyl phthalate, etc.),adipic acid esters and stearic acid may be added to these basematerials. The resin transpiration formulation can be prepared by mixingthe compound of the present invention with the base material, kneadingthe mixture, followed by molding it by injection molding, extrusionmolding or pressure molding. The resultant resin formulation can besubjected to further molding or cutting procedure, if necessary, to beprocessed into shapes such as a plate, film, tape, net or string shape.These resin formulations can be processed into animal collars, animalear tags, sheet products, trap strings, gardening supports and otherproducts.

Examples of a base material for the poison bait include bait ingredientssuch as grain powder, vegetable oil, saccharide and crystallinecellulose, antioxidants such as dibutylhydroxytoluene andnordihydroguaiaretic acid, preservatives such as dehydroacetic acid,accidental ingestion inhibitors for children and pets such as a chilipowder; insect attraction fragrances such as cheese flavor, onion flavorand peanut oil.

The pest control method of the present invention usually conducted byapplying an effective amount of the compound of the present invention toa pest or a habitat thereof (e.g. plant bodies, soil, the interior of ahouse, animal bodies, the interior of a car, or outdoor open space) in aform of a pest control agent of the present invention.

A method for applying the pest control agent of the present inventionincludes the following methods, and appropriately selected depending onthe form of the pest control agent of the present invention, theapplication area and so on.

(1) A method comprising applying a pest control agent of the presentinvention as it is to a pest or a habitat of the pest.

(2) A method comprising diluting a pest control agent of the presentinvention with a solvent such as water, and then spraying the dilutionto a pest or a habitat of the pest. In this method, the pest controlagent of the present invention is usually formulated into anemulsifiable concentrate, a wettable powder, a flowable formulation, amicrocapsule or the like. The formulation is usually diluted so that theconcentration of the compound of the present invention can be 0.1 to10,000 ppm.(3) A method comprising heating a pest control agent of the presentinvention at a habitat of a pest, thereby allowing an active ingredientto volatilize and diffuse from the pest control agent.In this case, any of the amount and concentration of application of thecompound of the present invention can be appropriately determineddepending on the form, application period, application area, applicationmethod, kind of a pest, damage to be incurred and so on.

When the compound of the present invention is used for prevention ofepidemics, the amount to be applied is usually from 0.0001 to 1,000mg/m³ of the compound of the present invention in the case of applyingto a space, and from 0.0001 to 1,000 mg/m² of the compound of thepresent invention in the case of applying to a plane. An insecticidalcoil or an electric insecticidal mat is applied by heating to volatilizeand diffuse an active ingredient, depending on the form of theformulation. A resin transpiration formulation, a paper transpirationformulation, an unwoven fabric transpiration formulation, a knit fabrictranspiration formulation or a sublimating tablet are allowed to standas it is in a space to be applied, and placed under air blowing.

When the pest control agent of the present invention is applied to aspace for the purpose of prevention of epidemics, examples of the spaceinclude a closet, a Japanese cabinet, a Japanese chest, a cupboard, atoilet, a bathroom, a shed, a living room, a dining room, a garage, theinterior of a car and so on. The pest control agent can be also appliedto outdoor open space.

When the pest control agent of the present invention is used forcontrolling external parasites of livestock such as cows, horses, pigs,sheep, goats and chickens and small animals such as dogs, cats, rats andmice, the pest control agent of the present invention can be applied tothe animals by a known method in the veterinary field. Specifically,when systemic control is intended, the pest control agent of the presentinvention is administered to the animals as a tablet, a mixture withfeed or a suppository, or by injection (including intramuscular,subcutaneous, intravenous and intraperitoneal injections). On the otherhand, when non-systemic control is intended, the pest control agent ofthe present invention is applied to the animals by means of spraying ofthe oil solution or aqueous solution, pour-on or spot-on treatment, orwashing of the animal with a shampoo formulation, or by putting a collaror ear tag made of the resin transpiration formulation to the animal. Inthe case of administering to an animal body, the dosage of the compoundof the present invention is usually in the range from 0.1 to 1,000 mgper 1 kg of an animal body weight.

When the pest control agent of the present invention is used forcontrolling a pest in the agricultural field, the amount can widely varydepending on the application period, application area, applicationmethod and other factors, and is usually in the range from 1 to 10,000 gin terms of the compound of the present invention per 10,000 m². Whenthe pest control agent of the present invention is formulated into anemulsifiable concentrate, a wettable powder, a flowable formulation andso on, the pest control agent is usually applied after diluting withwater so that the concentration of the active ingredient becomes 0.01 to10,000 ppm, and a granule or a dust is usually applied as it is.

These formulations or water dilutions of the formulations may bedirectly sprayed over pests or plants such as crop plants to beprotected from pests, or may be used in the soil treatment for thecontrol of pests which inhabit the soil of the cultivated land.

Application can also be conducted by a method of directly winding theresin formulation formed into sheet-shaped, or string- or cord-shapedformulation around plants, disposing the formulation in the neighborhoodof plants, or spreading the formulation on the soil surface at the root.

The compound of the present invention can be used as a pest controlagent in cultivating field such as farm, paddy field, lawn or orchard,or non-cultivating field. The compound of the present invention cancontrol pests inhabiting the cultivating field in the cultivating fieldwhere the following “plant crops” are cultivated.

Agricultural crops: corn, rice, wheat, barley, rye, oat, sorghum,cotton, soybean, peanut, sarrazin, sugar beet, rapeseed, sunflower,sugar cane, tobacco, etc.;

Vegetables: Solanaceae vegetables (eggplant, tomato, green pepper, hotpepper, potato etc.), Cucurbitaceae vegetables (cucumber, pumpkin,zucchini, watermelon, melon etc.), Cruciferae vegetables (Japaneseradish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, brownmustard, broccoli, cauliflower etc.), Compositae vegetables (burdock,garland chrysanthemum, artichoke, lettuce etc.), Liliaceae vegetables(Welsh onion, onion, garlic, asparagus etc.), Umbelliferae vegetables(carrot, parsley, celery, parsnip etc.), Chenopodiaceae vegetables(spinach, Swiss chard etc.), Labiatae vegetables (Japanese basil, mint,basil etc.), strawberry, sweat potato, yam, aroid, etc.;

Fruit trees: pomaceous fruits (apple, common pear, Japanese pear,Chinese quince, quince etc.), stone fleshy fruits (peach, plum,nectarine, Japanese plum, cherry, apricot, prune etc.), citrus plants(Satsuma mandarin, orange, lemon, lime, grapefruit etc.), nuts(chestnut, walnut, hazel nut, almond, pistachio, cashew nut, macadamianut etc.), berry fruits (blueberry, cranberry, blackberry, raspberryetc.), grape, persimmon, olive, loquat, banana, coffee, date, coconutpalm, oil palm, etc.;

Trees other than fruit trees: tea, mulberry, woody plants (azalea,camellia, hydrangea, sasanqua, Illicium religiosum, cherry tree, tuliptree, crape myrtle, fragrant olive etc.), street trees (ash tree, birch,dogwood, eucalyptus, ginkgo, lilac, maple tree, oak, poplar, cercis,Chinese sweet gum, plane tree, zelkova, Japanese arborvitae, fir tree,Japanese hemlock, needle juniper, pine, spruce, yew, elm, horse-chestnutetc.), sweet viburnum, Podocarpus macrophyllus, Japanese cedar, Japanesecypress, croton, spindle tree, Chainese howthorn, etc.

Lawn: zoysia (Japanese lawn grass, mascarene grass, etc.), Bermuda grass(Cynodon dactylon, etc.), bent grass (creeping bent grass, Agrostisstolonifera, Agrostis tenuis, etc.), bluegrass (Kentucky bluegrass,rough bluegrass, etc.), fescue (tall fescue, chewing fescue, creepingfescue, etc.), ryegrass (darnel, perennial ryegrass, etc.), cocksfoot,timothy grass, etc.;

Others: flowers (rose, carnation, chrysanthemum, Eustoma grandiflorumShinners (prairie gentian), gypsophila, gerbera, pot marigold, salvia,petunia, verbena, tulip, aster, gentian, lily, pansy, cyclamen, orchid,lily of the valley, lavender, stock, ornamental kale, primula,poinsttia, gladiolus, cattleya, daisy, verbena, cymbidium, begonia,etc.), bio-fuel plants (Jatropha, safflower, gold-of-pleasure,switchgrass, Miscanthus, ribbon grass, giant reed, kenaf, cassava,willow, etc.), foliage plant; etc.

The above “plant crops” include gene transgenic plant crops.

The compound of the present invention can be mixed with or can be usedin combination with other insecticide, acaricide, nematocide, soil pestcontrol agent, fungicide, herbicide, plant growth regulating agent,repellent, synergist, fertilizer, or soil modifier.

Examples of active ingredient of such the insecticide and acaricideinclude:

(1) Synthetic pyrethroid compounds:

acrinathrin, allethrin, beta-cyfluthrin, bifenthrin, cycloprothrin,cyfluthrin, cyhalothrin, cypermethrin, empenthrin, deltamethrin,esfenvalerate, ethofenprox, fenpropathrin, fenvalerate, flucythrinate,flufenoprox, flumethrin, fluvalinate, halfenprox, imiprothrin,permethrin, prallethrin, pyrethrins, resmethrin, sigma-cypermethrin,silafluofen, tefluthrin, tralomethrin, transfluthrin, tetramethrin,phenothrin, cyphenothrin, alpha-cypermethrin, zeta-cypermethrin,lambda-cyhalothrin, gamma-cyhalothrin, furamethrin, tau-fluvalinate,metofluthrin,2,3,5,6-tetrafluoro-4-methylbenzyl=2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylate,2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl=2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate,2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl=2,2,3,3-tetramethylcyclopropanecarboxylate, and so on;

(2) Organic phosphorous compounds:

acephate, Aluminium phosphide, butathiofos, cadusafos, chlorethoxyfos,chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, cyanophos: CYAP,diazinon, DCIP (dichlorodiisopropyl ether), dichlofenthion:ECP,dichlorvos:DDVP, dimethoate, dimethylvinphos, disulfoton, EPN, ethion,ethoprophos, etrimfos, fenthion:MPP, fenitrothion:MEP, fosthiazate,formothion, Hydrogen phosphide, isofenphos, isoxathion, malathion,mesulfenfos, methidathion:DMTP, monocrotophos, naled:BRP,oxydeprofos:ESP, parathion, phosalone, phosmet:PMP, pirimiphos-methyl,pyridafenthion, quinalphos, phenthoate:PAP, profenofos, propaphos,prothiofos, pyraclorfos, salithion, sulprofos, tebupirimfos, temephos,tetrachlorvinphos, terbufos, thiometon, trichlorphon:DEP, vamidothion,phorate, cadusafos, and so on;

(3) Carbamate compounds:

alanycarb, bendiocarb, benfuracarb, BPMC, carbaryl, carbofuran,carbosulfan, cloethocarb, ethiofencarb, fenobucarb, fenothiocarb,fenoxycarb, furathiocarb, isoprocarb:MIPC, metolcarb, methomyl,methiocarb, NAC, oxamyl, pirimicarb, propoxur:PHC, XMC, thiodicarb,xylylcarb, aldicarb, and so on;

(4) Nereistoxin compounds:

cartap, bensultap, thiocyclam, monosultap, bisultap, and so on;

(5) Neonicotinoid compounds:

imidacloprid, nitenpyram, acetamiprid, thiamethoxam, thiacloprid,dinotefuran, clothianidin, and so on;

(6) Benzoylurea compounds:

chlorfluazuron, bistrifluoron, diafenthiuron, diflubenzuron, fluazuron,flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron,noviflumuron, teflubenzuron, triflumuron, triazuron, and so on;

(7) Phenylpyrazole compounds:

acetoprole, ethiprole, fipronil, vaniliprole, pyriprole, pyrafluprole,and so on;

(8) Bt toxin insecticides:

Live spores derived from and crystal toxins produced from Bacillusthuringiesis and a mixture thereof;

(9) Hydrazine compounds:

chromafenozide, halofenozide, methoxyfenozide, tebufenozide, and so on;

(10) Organic chlorine compound:

aldrin, dieldrin, dienochlor, endosulfan, methoxychlor, and so on;

(11) Natural insecticides:

machine oil, nicotine-sulfate;

(12) Other insecticides:

avermectin-B, bromopropylate, buprofezin, chlorphenapyr, cyromazine,D-D(1,3-Dichloropropene), emamectin-benzoate, fenazaquin, flupyrazofos,hydroprene, methoprene, indoxacarb, metoxadiazone, milbemycin-A,pymetrozine, pyridalyl, pyriproxyfen, spinosad, sulfluramid,tolfenpyrad, triazamate, flubendiamide, lepimectin, Arsenic acid,benclothiaz, Calcium cyanamide, Calcium polysulfide, chlordane, DDT,DSP, flufenerim, flonicamid, flurimfen, formetanate, metam-ammonium,metam-sodium, Methyl bromide, Potassium oleate, protrifenbute,spiromesifen, Sulfur, metaflumizone, spirotetramat, pyrifluquinazone,spinetoram, chlorantraniliprole, tralopyril, and so on.

Examples of the active ingredient of the repellent includeN,N-diethyl-m-toluamide, limonene, linalool, citronellal, menthol,menthone, hinokitiol, geraniol, eucalyptol, indoxacarb, carane-3,4-diol,MGK-R-326, MGK-R-874 and BAY-KBR-3023.

Examples of the active ingredient of the synergist include5-[2-(2-butoxyethoxy)ethoxymethyl]-6-propyl-1,3-benzodioxol,N-(2-ethylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylmide,octachlorodipropylether, thiocyanoacetic acidisobornyl,N-(2-ethylhexyl)-1-isopropyl-4-methylbicyclo[2.2.2]oct-5-ene-2,3-dicarboxylmide.

EXAMPLES

The present invention will be further described in more detail below byway of Production Examples, Reference Production Examples, FormulationExamples and Test Examples, but the present invention is not limited tothese Examples.

First, Production Examples of the compound of the present invention areshown below. In ¹H-NMR, the description “1.21+1.22 (s+s, 3H)” means thatpeaks of singlet(s) exist at 1.21 ppm and 1.22 ppm, and the total ofintegral values of these two peaks is 3H, for example.

Production Example 1

To a chloroform solution (20 mL) of2-hydroxymethyl-5-methyl-4-(2-propynyl)-2,4-dihydro-[1,2,4]triazol-3-one(1.00 g, 6.00 mmol) and(1R)-trans-3-[(1EZ)-2-cyano-2-(methylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylicacid (1.26 g, 5.97 mmol), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimidehydrochloride (1.60 g, 8.35 mmol) and 4-dimethylaminopyridine (30 mg)were added. After stirring the mixture at room temperature for 48 hours,water was poured into the reaction mixture and the solution wasextracted with ethyl acetate. The organic layer was dried over magnesiumsulfate and then concentrated under reduced pressure, and the residuewas subjected to silica gel chromatography to obtain 1.35 g of3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]triazolylmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(methylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate (E:Z=50:50) (hereinafter referred to as the compound of thepresent invention (1)) represented by the following formula:

was obtained.

Pale yellow liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.20+1.21 (s+s, 3H),1.32+1.34 (s+s, 3H), 1.79 to 1.82 (d, 1H), 2.35 (s, 3H), 2.37 (m, 1H),2.40+2.46 (s+s, 3H), 2.49 to 2.53 (m, 1H), 4.44 (d, 2H, 2.4 Hz), 5.67 to5.82 (m, 2H), 6.13 (d, 0.5H, J=10.0 Hz), 6.17 (d, 0.5H, J=10.0 Hz)

Production Example 2

3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]triazolylmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(methylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate obtained in Production Example 1 was purified into an Eisomer and a Z isomer by silica gel column chromatography (eluent:hexane/ethyl acetate=2:1) to obtain, as a fraction having higherpolarity,3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]triazolylmethyl=(1R)-trans-3-[(1E)-2-cyano-2-(methylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate (hereinafter referred to as the compound of the presentinvention (2)) represented by the following formula:

White crystal, melting point of 104.0 to 105.0° C.: ¹H-NMR (CDCl₃, TMS)δ (ppm): 1.21 (s, 3H), 1.34 (s, 3H), 1.81 (d, 1H, J=5.2 Hz), 2.35 (s,3H), 2.37 (m, 1H), 2.40 (s, 3H), 2.49 to 2.53 (dd, 1H), 4.44 (d, 2H, 2.8Hz), 5.75 (dd, 2H), 6.13 (d, 1H, J=10.0 Hz)

Production Example 3

The operation was conducted in the same manner as Production Example 1,except that2-hydroxymethyl-5-methyl-4-(2-propynyl)-2,4-dihydro-[1,2,4]triazol-3-onewas used in place of3-hydroxymethyl-1-(2-propynyl)imidazolidin-2,4-dione, and(1R)-trans-3-[(1EZ)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylicacid was used in place of(1R)-trans-3-[(1EZ)-2-cyano-2-(methylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylicacid,3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]triazolylmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate (E:Z=50:50) (hereinafter referred to as the compound of thepresent invention (3)) represented by the following formula:

was obtained.

Pale yellow liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.20 to 1.37 (m, 9H,E+Z isomer), 1.81 (d, 0.5H, Z isomer), 1.83 (d, 0.5H, E isomer), 2.36(s, 3H), 2.37 (m, 1H), 2.53 (m, 1H), 2.84 (q, 1H, E isomer), 2.91 (q,1H, Z isomer), 4.43 (d, 2H), 5.67 to 5.82 (m, 2H), 6.20 (d, 0.5H, Eisomer), 6.24 (d, 0.5H, Z isomer)

Production Example 4

3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]triazolylmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate obtained in Production Example 3 was subjected to silica gelcolumn chromatography (eluent: hexane/ethyl acetate=2:1) to obtain, as afraction having higher polarity,3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]triazolylmethyl=(1R)-trans-3-[(1E)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate (hereinafter referred to as the compound of the presentinvention (4)) represented by the following formula:

Pale yellow liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.21 (s, 3H), 1.30 (t,3H), 1.34 (s, 3H), 1.83 (d, 1H), 2.36 (s, 3H), 2.37 (m, 1H), 2.53 (dd,1H), 2.84 (q, 2H), 4.44 (d, 2H), 5.75 (dd, 2H), 6.20 (d, 1H)

Production Example 5

3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]triazolylmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate obtained in Production Example 3 was subjected to silica gelcolumn chromatography (eluent: hexane/ethyl acetate=2:1) to obtain, as afraction having lower polarity,3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]triazolylmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate (E:Z=33:67) (hereinafter referred to as the compound of thepresent invention (5)) represented by the following formula:

Pale yellow liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.20 (s, 3H), 1.32 (s,3H), 1.31 to 1.34 (t, 3H), 1.81 (d, 0.67H, Z isomer), 1.83 (d, 0.33H, Eisomer), 2.36 (s, 3H), 2.37 (m, 1H), 2.54 (m, 1H), 2.91 (q, 1H), 4.43(d, 2H), 5.67 to 5.82 (m, 2H), 6.20 (d, 0.33H, E isomer), 6.24 (d,0.67H, Z isomer)

Production Example 6

3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]triazolylmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(methylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate obtained in Production Example 1 was subjected to silica gelcolumn chromatography (eluent: hexane/ethyl acetate=2:1) to obtain, as afraction having higher polarity,3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]triazolylmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(methylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate (E:Z=80:20) (hereinafter referred to as the compound of thepresent invention (6)) represented by the following formula:

was obtained.

Pale yellow liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.20+1.21 (s+s, 3H),1.32+1.34 (s+s, 3H), 1.79 to 1.82 (d, 1H), 2.35 (s, 3H), 2.37 (m, 1H),2.40+2.46 (s+s, 3H), 2.49 to 2.53 (m, 1H), 4.44 (d, 2H, 2.4 Hz), 5.67 to5.82 (m, 2H), 6.13 (d, 0.8H, J=10.0 Hz), 6.17 (d, 0.2H, J=10.0 Hz)

Production Example 7

3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]triazolylmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate obtained in Production Example 3 was subjected to silica gelcolumn chromatography (eluent: hexane/ethyl acetate=2:1) to obtain, as afraction having higher polarity,3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]triazolylmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate (E:Z=90:10) (hereinafter referred to as the compound of thepresent invention (7)) represented by the following formula:

Pale yellow liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.20 (s, 3H), 1.32 (s,3H), 1.31 to 1.34 (t, 3H), 1.81 (d, 0.1H, Z isomer), 1.83 (d, 0.9H, Eisomer), 2.36 (s, 3H), 2.37 (m, 1H), 2.54 (m, 1H), 2.91 (q, 1H), 4.43(d, 2H), 5.67 to 5.82 (m, 2H), 6.20 (d, 0.9H, E isomer), 6.24 (d, 0.1H,Z isomer)

Production Example 8

3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]triazolylmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate obtained in Production Example 3 was subjected to silica gelcolumn chromatography (eluent: hexane/ethyl acetate=2:1) to obtain, as afraction having higher polarity,3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]triazolylmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate (E:Z=80:20) (hereinafter referred to as the compound of thepresent invention (8)) represented by the following formula:

Pale yellow liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.20 (s, 3H), 1.32 (s,3H), 1.31 to 1.34 (t, 3H), 1.81 (d, 0.2H, Z isomer), 1.83 (d, 0.8H, Eisomer), 2.36 (s, 3H), 2.37 (m, 1H), 2.54 (m, 1H), 2.91 (q, 1H), 4.43(d, 2H), 5.67 to 5.82 (m, 2H), 6.20 (d, 0.8H, E isomer), 6.24 (d, 0.2H,Z isomer)

With respect to the production of the carboxylic acid compound (3) orthe like, Reference Production Examples are shown below.

Reference Production Example 1

Methyl=(1R)-trans-3-formyl-2,2-dimethylcyclopropane carboxylate (6.41 g,41.1 mmol), methylthioacetonitrile (3.94 g, 45.2 mmol) and potassiumcarbonate (6.24 g, 45.2 mmol) were added to a mixture ofN,N-dimethylformamide (40 mL) and toluene (15 mL), followed by stirringit at 100° C. for 3 hours. The reaction mixture cooled to roomtemperature was added to 200 ml of ice water, and the solution wasextracted twice with ethyl acetate (100 mL each). The obtained ethylacetate layers were combined, washed once with saturated brine (50 mL)and then dried over magnesium sulfate. After concentration of theorganic layer under reduced pressure, the residue was subjected tosilica gel chromatography to obtain 8.23 g ofmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(methylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate represented by the following formula:

Colorless liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.23+1.24 (s+s, 3H),1.32+1.33 (s+s, 3H), 1.79+1.80 (d+d, 1H, J=5.2 Hz), 2.40+2.46 (s+s, 3H),2.50 to 2.53 (m, 1H), 3.70 (s, 3H), 6.18+6.21 (d+d, 1H, J=10.0 Hz)

Reference Production Example 2

Methyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(methylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate (2.29 g, 10.2 mmol) was dissolved in a mixture of methanol(6 mL) and water (10 mL), and potassium hydroxide (1.1 g, 19.6 mmol) wasadded thereto, followed by stirring it at room temperature for 12 hours.The reaction mixture was added to ice water (30 mL), and the solutionwas extracted with ethyl acetate (20 mL). To the obtained aqueous layer,hydrochloric acid was added until the pH became 2, followed byextraction twice with ethyl acetate (30 mL). The obtained ethyl acetatelayers were combined, washed twice with saturated brine (30 mL) and thendried over magnesium sulfate. After concentration of the organic layerunder reduced pressure, 2.08 g of(1R)-trans-3-[(1EZ)-2-cyano-2-(methylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylicacid represented by the following formula:

was obtained.

Pale yellow crystal: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.24+1.25 (s+s, 3H),1.36+1.37 (s+s, 3H), 1.79+1.81 (d+d, 1H, J=5.2 Hz), 2.41+2.47 (s+s, 3H),2.50 to 2.56 (m, 1H), 6.17+6.21 (d+d, 1H, E+Z, J=10.4 Hz)

Reference Production Example 3

Chloroacetonitrile (4.0 g, 53.0 mmol) and potassium carbonate (8.8 g,63.8 mmol) were added to N,N-dimethylformamide (30 mL) and ethylmercaptan (3.7 mL, 49.9 mmol) was added thereto under ice cooling,followed by stirring it at room temperature for 24 hours. Thereafter,methyl=(1R)-trans-3-formyl-2,2-dimethylcyclopropane carboxylate (8.20 g,52.6 mmol) and potassium carbonate (9.0 g, 65.2 mmol) were added,followed by further stirring it at room temperature for 24 hours. Thereaction mixture was added to ice water (100 mL), and the solution wasextracted twice with ethyl acetate (100 mL each). The obtained ethylacetate layers were combined, washed once with saturated brine (50 mL)and then dried over magnesium sulfate. After concentration of theorganic layer under reduced pressure, the residue was subjected tosilica gel chromatography to obtain 9.93 g ofmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate represented by the following general formula:

Colorless liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.23+1.24 (s+s, 3H), 1.26to 1.33 (m, 3H), 1.33+1.35 (s+s, 3H), 1.79 to 1.83 (m, 1H), 2.50 to 2.55(m, 1H), 2.84 to 2.90 (m, 2H), 3.71 (s, 3H), 6.25 to 6.29 (m, 1H)

Reference Production Example 4

After dissolvingmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate (9.90 g, 41.4 mmol) in a mixture of methanol (15 mL) andwater (5 mL), potassium hydroxide (3.5 g, 62.5 mmol) was added thereto,followed by stirring it at room temperature for 12 hours. The reactionmixture was added to ice water (60 mL), and the solution was extractedwith ethyl acetate (50 mL) To the obtained aqueous layer, hydrochloricacid was added until the pH became 2, followed by extraction twice withethyl acetate (50 mL). The obtained ethyl acetate layers were combined,washed twice with saturated brine (50 mL) and then dried over magnesiumsulfate. After concentration of the organic layer under reducedpressure, 8.98 g of(1R)-trans-3-[(1EZ)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylicacid represented by the following formula:

was obtained.

Reference Production Example 5

Tomethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylicacid (8.98 g, 39.9 mmol), toluene (25 mL) was added and then thionylchloride (5.0 g, 42.0 mmol) was added. Furthermore,N,N-dimethylformamide (50 mg) was added, followed by stirring at aninner temperature of 60 to 70° C. for 4 hours. The reaction mixture wasconcentrated under reduced pressure to obtain 9.62 g of(1R)-trans-3-[(1EZ)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylicacid chloride represented by the following formula:

Reference Production Example 6

The reaction was conducted in the same manner as Reference ProductionExample 3, except that propyl mercaptan was used in place of ethylmercaptan,methyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(propylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate represented by the following formula:

was obtained.

Colorless liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 0.99 to 1.00 (m, 3H),1.23+1.24 (s+s, 3H), 1.33+1.35 (s+s, 3H), 1.62 to 1.70 (m, 2H), 1.79 to1.82 (m, 1H), 2.50 to 2.56 (m, 1H), 2.80 to 2.89 (m, 2H), 3.71 (s, 3H),6.23 to 6.28 (m, 1H)

Reference Production Example 7

The reaction was conducted in the same manner as Reference ProductionExample 4, except thatmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(propylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate was used in place ofmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate,(1R)-trans-3-[(1EZ)-2-cyano-2-(propylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylicacid represented by the following formula:

was obtained.

Pale yellow solid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 0.99 to 1.04 (m, 3H),1.25+1.26 (s+s, 3H), 1.36+1.37 (s+s, 3H), 1.62 to 1.70 (m, 2H), 1.79 to1.83 (m, 1H), 2.53 to 2.56 (m, 1H), 2.80 to 2.90 (m, 2H), 6.23 to 6.28(m, 1H)

Reference Production Example 8

The reaction was conducted in the same manner as Reference ProductionExample 3, except that butyl mercaptan was used in place of ethylmercaptan,methyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(butylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate represented by the following formula:

was obtained.

Colorless liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 0.92 to 0.95 (m, 3H),1.22+1.23 (s+s, 3H), 1.32+1.33 (s+s, 3H, 1.41 to 1.65 (m, 4H), 1.79 to1.82 (m, 1H), 2.52 to 2.56 (m, 1H), 2.80 to 2.91 (m, 2H), 3.71 (s, 3H),6.22 to 6.28 (m, 1H)

Reference Production Example 9

The reaction was conducted in the same manner as Reference ProductionExample 4, except thatmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(butylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate was used in place ofmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate,(1R)-trans-3-[(1EZ)-2-cyano-2-(butylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylicacid represented by the following formula:

was obtained.

Pale yellow solid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 0.99 to 1.04 (m, 3H),1.25+1.26 (s+s, 3H), 1.36+1.37 (s+s, 3H), 1.40 to 1.70 (m, 4H), 1.79 to1.83 (m, 1H), 2.53 to 2.58 (m, 1H), 2.81 to 2.92 (m, 2H), 6.22 to 6.28(m, 1H)

Reference Production Example 10

The reaction was conducted in the same manner as Reference ProductionExample 3, except that isopropyl mercaptan was used in place of ethylmercaptan,methyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(isopropylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate represented by the following formula:

was obtained.

Colorless liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.23 to 1.39 (m, 12H),1.81 to 1.85 (m, 1H), 2.51 to 2.62 (m, 1H), 3.31 to 3.45 (m, 1H),3.71+3.72 (s+s, 3H), 6.27 to 6.36 (m, 1H)

Reference Production Example 11

The reaction was conducted in the same manner as Reference ProductionExample 4, except thatmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(isopropylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate was used in place ofmethyl=(1R)-trans-3-[(1EZ)-2-cyano-2-(ethylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylate,(1R)-trans-3-[(1EZ)-2-cyano-2-(isopropylthio)ethenyl]-2,2-dimethylcyclopropanecarboxylicacid represented by the following formula:

was obtained.

Reference Production Example 12

(1R)-4-hydroxy-6,6-dimethyl-3-oxabicyclo[3.1.0]hexan-2-one (1.585 g,11.2 mmol), methylthioacetonitrile (1.30 g, 14.9 mmol) and potassiumcarbonate (1.85 g, 13.4 mmol) were added to N,N-dimethylformamide (15mL), followed by stirring it at 20° C. for 48 hours. The reactionmixture was added to ice water (50 mL), and the solution was extractedwith ethyl acetate (50 mL). To the obtained aqueous layer, 5%hydrochloric acid was added until the pH became 2, and then the aqueouslayer was extracted twice with ethyl acetate (60 ml each). The obtainedethyl acetate layers were combined, washed once with saturated brine (50mL) and then dried over magnesium sulfate. After concentration of theorganic layer under reduced pressure, 2.30 g of2-((1S,5R)-6,6-dimethyl-4-oxo-3-oxabicyclo[3.1.0]hexan-2-yl)-2-(methylthio)acetonitrilerepresented by the following formula:

was obtained.

Pale yellow liquid: ¹H-NMR (CDCl₃, TMS) δ (ppm): 1.22 to 1.31 (m, 6H),1.44 (m, 1H), 1.77 (m, 1H), 2.35 (s, 1.5H), 2.38 (s, 1.5H), 3.60 (d,0.5H), 3.64 (d, 0.5H), 4.23 (m, 0.5H), 4.33 (m, 0.5H)

Formulation Examples are shown below. Parts are by mass.

Formulation Example 1

Twenty (20) parts of each of the compounds (1) to (8) of the presentinvention is dissolved in 65 parts of xylene and 15 parts of SOLPOL3005X (a registered trademark of TOHO Chemical Industry Co., Ltd.) isadded thereto and thoroughly mixed with stirring to obtain emulsifiableconcentrates.

Formulation Example 2

Five (5) parts of SORPOL 3005X is added to 40 parts of each of thecompounds (1) to (8) of the present invention and the mixture isthoroughly mixed, and 32 parts of CARPLEX #80 (synthetic hydratedsilicon oxide, a registered trademark of SHIONOGI & CO., LTD.) and 23parts of 300-mesh diatomaceous earth are added thereto, followed bymixing with stirring by a mixer to obtain wettable powders.

Formulation Example 3

A mixture of 1.5 parts of each of the compounds (1) to (8) of thepresent invention, 1 part of TOKUSIL GUN (synthetic hydrated siliconoxide, manufactured by Tokuyama Corporation), 2 parts of REAX 85A(sodium lignin sulfonate, manufactured by West Vaco Chemicals), 30 partsof BENTONITE FUJI (bentonite, manufactured by Houjun) and 65.5 parts ofSHOUKOUZAN A clay (kaoline clay, manufactured by Shoukouzan Kougyousho)is thoroughly pulverized and mixed, and water is added thereto. Themixture is thoroughly kneaded, granulated by an extruding granulator,and then dried to obtain 1.5% granules.

Formulation Example 4

To a mixture of 10 parts of each of the compounds (1) to (8) of thepresent invention, 10 parts of phenylxylylethane and 0.5 part of SUMIDURL-75 (tolylene diisocyanate, manufactured by Sumitomo Bayer UrethaneCo., Ltd.) is added 20 parts of 10% aqueous solution of gum arabic, andthe mixture is stirred with a homomixer to obtain an emulsion having anaverage particle diameter of 20 μm. To the emulsion, 2 parts of ethyleneglycol is added and the mixture is further stirred in a warm bath at atemperature of 60° C. for 24 hours to obtain microcapsule slurry. On theother hand, 0.2 part of xanthan gum and 1.0 part of VEEGUM R (aluminummagnesium silicate, manufactured by Sanyo Chemical Industries, Ltd.) aredispersed in 56.3 parts of ion-exchanged water to obtain a thickenersolution. Then, 42.5 parts of the above-mentioned microcapsule slurryand 57.5 parts of the above-mentioned thickener solution are mixed toobtain microcapsules.

Formulation Example 5

A mixture of 10 parts of each of the compounds (1) to (8) of the presentinvention and 10 parts of phenylxylylethane is added to 20 parts of a10% aqueous solution of polyethylene glycol, and the mixture is stirredby a homomixer to obtain an emulsion having an average particle diameterof 3 μm. On the other hand, 0.2 part of xanthan gum and 1.0 part ofVEEGUM R (aluminum magnesium silicate, manufactured by Sanyo ChemicalIndustries, Ltd.) are dispersed in 58.8 parts of ion-exchanged water toobtain a thickener solution. Then, 40 parts of the above-mentionedemulsion solution and 60 parts of the above-mentioned thickener solutionare mixed to obtain flowable formulations.

Formulation Example 6

To 5 parts of each of the compounds (1) to (8) of the present invention,3 parts of CARPLEX #80 (synthetic hydrated silicon oxide, a registeredtrademark of SHIONOGI & CO., LTD.), 0.3 part of PAP (a mixture ofmonoisopropyl phosphate and diisopropyl phosphate) and 91.7 parts oftalc (300 mesh) are added and the mixture is stirred by a mixer toobtain dusts.

Formulation Example 7

Zero point one (0.1) part of each of the compounds (1) to (8) of thepresent invention is dissolved in 10 parts of dichloromethane and thesolution is mixed with 89.9 parts of deodorized kerosine to obtain oilsolutions.

Formulation Example 8

Zero point one (0.1) part of each of the compounds (1) to (8) of thepresent invention and 39.9 parts of deodorized kerosine are mixed anddissolved, and the solution is filled into an aerosol container and avalve portion is installed. Then, 60 parts of power propellant(liquefied petroleum gas) is filled therein under pressure through thevalve portion to obtain oil-based aerosol formulations.

Formulation Example 9

Zero point six (0.6) part of each of the compounds (1) to (8) of thepresent invention, 5 parts of xylene, 3.4 parts of deodorized kerosineand 1 part of Reodol MO-60 (emulsifier, a registered trademark of KaoCorporation) are mixed and dissolved, and the solution and 50 parts ofwater are filled into an aerosol container, and then 40 parts of powerpropellant (liquefied petroleum gas) is filled therein under pressurethrough a valve portion to obtain aqueous aerosol formulations.

Formulation Example 10

Zero point three (0.3) g of each of the compounds (1) to (8) of thepresent invention is dissolved in 20 ml of acetone and the solution isuniformly mixed with stirring with 99.7 g of a base material for a coil(obtained by mixing Tabu powder, Pyrethrum marc and wooden powder at aratio of 4:3:3). Then, 100 ml of water is added thereto, and the mixtureis thoroughly kneaded, dried and molded to obtain insecticidal coils.

Formulation Example 11

A mixture of 0.8 g of each of the compounds (1) to (8) of the presentinvention and 0.4 g of piperonyl butoxide is dissolved in acetone andthe total volume is adjusted to 10 ml. Then, 0.5 ml of this solution isuniformly impregnated into a base material for an insecticidal mat forelectric heating (a plate obtained by hardening fibrils of a mixture ofcotton linters and pulp) having a size of 2.5 cm×1.5 cm and a thicknessof 0.3 cm to obtain insecticidal mats for electric heating.

Formulation Example 12

A solution obtained by dissolving 3 parts of each of the compound (1) to(8) of the present invention in 97 parts of deodorized kerosine ispoured into a vessel made of vinyl chloride. A liquid absorptive corewhose upper part can be heated by a heater (an inorganic pulverizedpowder is hardened with a binder and sintered) is inserted thereinto toobtain parts to be used for a liquid absorptive core type thermaltranspiring apparatus.

Formulation Example 13

One hundred (100) mg of each of the compound (1) to (8) of the presentinvention is dissolved in an appropriate amount of acetone and thesolution is impregnated into a porous ceramic plate having a size of 4.0cm×4.0 cm and a thickness of 1.2 cm to obtain thermal fumigants.

Formulation Example 14

One hundred (100) μg of each of the compound (1) to (8) of the presentinvention is dissolved in an appropriate amount of acetone and thesolution is uniformly applied to filter paper having a size of 2 cm×2 cmand a thickness of 0.3 mm, and air-dried to remove acetone, and thusvolatile agents for using at room temperature are obtained.

Formulation Example 15

Ten (10) parts of each of the compound of the present inventions (1) to(8), 35 parts of white carbon containing 50 parts of a polyoxyethylenealkyl ether sulfate ammonium salt, and 55 parts of water are mixed andthen finely ground by a wet grinding method to obtain 10% formulations.

The following Test Examples illustrate that the compounds of the presentinvention are effective as an active ingredient of a pest control agent.

Test Example 1

Zero point one (0.1) part of the compound of the present inventions (1),(2) and (4) was dissolved in 10 parts of isopropyl alcohol and thesolution was mixed with 89.9 parts of deodorized kerosene to prepare a0.1% (w/v) oil solution.

Six adult American cockroaches (Periplaneta Americana, 3 males and 3females) were released in a test container (diameter 12.5 cm, 10 cmhigh, the bottom face is made of 16 mesh metallic wire), the inner faceon which butter was applied, and the container was set at the bottom ofa test chamber (bottom face: 46 cm×46 cm, height: 70 cm). Each 1.5 ml ofthe oil solution of the compound of the present invention (1), (2) and(4) was sprayed using a spray gun at a pressure of 0.4 kg/cm² from 60 cmhigher than the upper face of the container. Thirty seconds after thespraying, the container was pulled out from the chamber. After aprescribed time, the number of knocked-down cockroaches was counted anda knock-down ratio was determined (repeated twice). The knocked-downratio was calculated by the following equation.Knocked-down ratio(%)=(Number of knocked-down cockroaches/Number of testcockroaches)×100

For comparison, the test was conducted in the same manner as the above,except for using2,5-dioxo-3-(2-propynyl)imidazolidinylmethyl=(1R)-cis-3-((Z)-2-cyano-2-methoxyethenyl)-2,2-dimethylcyclopropanecarboxylate (compound described in JP-A-60-16962, hereinafter referredto as the comparative compound (1)) represented by the followingformula:

and3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]triazolylmethyl=(1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (compound described in JP-A-57-158765, hereinafter referredto as the comparative compound (2)) represented by the followingformula:

The results (2 minutes after spraying) are shown in Table 1.

TABLE 1 Knock-down ratio (%) Test compound 2 minutes after sprayingcompound of the present 100 invention (1) compound of the present 92invention (2) compound of the present 100 invention (4) comparativecompound (1) 42 comparative compound (2) 33

Test Example 2

Zero point zero two five (0.025) part of the compound of the presentinvention (1) and (4) was dissolved in 10 parts of isopropyl alcohol,and the solution was mixed with 89.975 parts of deodorized kerosene toprepare a 0.025% (w/v) oil solution.

Ten adult female common mosquitoes (Culex pipens pallens) were releasedin a cubic glass chamber having each side of 70 cm. The oil solution ofthe compound of the present invention (1) and (4) was sprayed into thechamber through a small window on the side of the chamber using aspraying gun at a pressure of 0.9 kg/cm². One minutes after spraying,the number of knocked-down mosquitoes was counted and a knock-down ratiowas determined. A knocked-down ratio was calculated by the followingequation.Knocked-down ratio(%)=(Number of knocked-down mosquitoes/Number of testmosquitoes)×100

The results are shown in Table 2.

TABLE 2 Knock-down ratio (%) Test compound 1 minutes after sprayingcompound of the present 95 invention (1) compound of the present 100invention (4)

Test Example 3

Zero point zero two five (0.025) part of the compound of the presentinvention (1) and (4) was dissolved in 10 parts of isopropyl alcohol,and the solution was mixed with 89.9975 parts of deodorized kerosene toprepare a 0.025% (w/v) oil solution.

Ten adult houseflies (Musca domestica) were released in a cubic glasschamber having each side of 70 cm, and 0.7 ml of the oil solution of thecompound of the present invention (1) and (4) was sprayed into thechamber through a small window on the side of the chamber using aspraying gun at a pressure of 0.9 kg/cm². Five minutes after spraying,the number of knocked-down flies was counted and a knock-down ratio wasdetermined. A knocked-down ratio was calculated by the followingequation.Knocked-down ratio(%)=(Number of knocked-down flies/Number of testflies)×100

The results are shown in Table 3.

TABLE 3 Knock-down ratio (%) Test compound 5 minutes after sprayingcompound of the present 80 invention (1) compound of the present 80invention (4)

Test Example 4

One (1) part of the compound of the present inventions (1) is dissolvedin 10 parts of isopropyl alcohol and the solution is mixed with 89 partsof deodorized kerosene to prepare a 1% (w/v) oil solution.

Ten adult female common mosquitoes (Culex pipens pallens) are releasedin a test container (bottom diameter 10.5 cm, 7 cm high, 650 ml) and atop of the cup is covered with a net. The cup is set at the bottom of atest chamber (bottom face: 46 cm×46 cm, height: 70 cm). Zero point five(0.5) ml of the oil solution of the compound of the present invention(1) is sprayed using a spray gun at a pressure of 0.4 kg/cm² from 30 cmhigher than the upper face of the cup. Immediately after spraying, thecup is pulled out from the test chamber. Two minutes after spraying, thenumber of knocked-down mosquitoes is counted and a knock-down ratio isdetermined.

Test Example 5

One (1) part of the compound of the present inventions (1) is dissolvedin 10 parts of isopropyl alcohol and the solution is mixed with 89 partsof deodorized kerosene to prepare a 1% (w/v) oil solution.

Ten adult houseflies (Musca domestica) are released in a test container(bottom diameter 10.5 cm, 7 cm high, 650 ml) and a top of the cup iscovered with a net. The cup is set at the bottom of a test chamber(bottom face: 46 cm×46 cm, height: 70 cm). Zero point five (0.5) ml ofthe oil solution of the compound of the present invention (1) is sprayedusing a spray gun at a pressure of 0.4 kg/cm² from 30 cm higher than theupper face of the cup. Immediately after spraying, the cup is pulled outfrom the test chamber. Two minutes after spraying, the number ofknocked-down mosquitoes is counted and a knock-down ratio wasdetermined.

Test Example 6

One (1) part of the compound of the present invention (1) is dissolvedin 10 parts of isopropyl alcohol and the solution is mixed with 89 partsof deodorized kerosene to prepare a 0.1% (w/v) oil solution.

Six adult American cockroaches (Periplaneta fuliginosa, 3 males and 3females) are released in a test container (diameter 12.5 cm, 10 cm high,the bottom face is made of 16 mesh metallic wire), the inner face onwhich butter is applied, and the container is set at the bottom of atest chamber (bottom face: 46 cm×46 cm, height: 70 cm). One point five(1.5) ml of the oil solution of the compound of the present invention(1) is sprayed using a spray gun at a pressure of 0.4 kg/cm² from 60 cmhigher than the upper face of the container. Thirty seconds after thespraying, the container is pulled out from the chamber. One minutesafter spraying, the number of knocked-down cockroaches is counted and aknock-down ratio was determined (repeated twice).

Test Example 7

Zero point one (0.1) part of the compound of the present inventions (1),(2) and (4) was dissolved in 10 parts of isopropyl alcohol and thesolution was mixed with 89.9 parts of deodorized kerosene to prepare a0.1% (w/v) oil solution.

Six adult American cockroaches (Periplaneta Americana, 3 males and 3females) were released in a test container (diameter 12.5 cm, 10 cmhigh, the bottom face is made of 16 mesh metallic wire), the inner faceon which butter was applied, and the container was set at the bottom ofa test chamber (bottom face: 46 cm×46 cm, height: 70 cm). Each 1.5 ml ofthe oil solution of the compound of the present invention (1), (2) and(4) was sprayed using a spray gun at a pressure of 0.4 kg/cm² from 60 cmhigher than the upper face of the container. Thirty seconds after thespraying, the container was pulled out from the chamber. Three minutesafter spraying, the number of knocked-down cockroaches was counted and aknock-down ratio was determined (repeated twice). The knocked-down ratiowas calculated by the following equation.Knocked-down ratio(%)=(Number of knocked-down cockroaches/Number of testcockroaches)×100

The results (3 minutes after spraying) are shown in Table 4.

TABLE 4 Knock-down ratio (%) Test compound 3 minutes after sprayingcompound of the present 100 invention (1) compound of the present 100invention (2) compound of the present 100 invention (4)

Test Example 8

Zero point zero zero six two five (0.00625) part of the compound of thepresent inventions (1), (2), (3), (4) and (5) was dissolved in 10 partsof isopropyl alcohol and the solution was mixed with 89.99375 parts ofdeodorized kerosene to prepare a 0.00625% (w/v) oil solution.

Ten adult German cockroaches (Blattella germanica, 5 males and 5females) were released in a test container (diameter 8.75 cm, 7.5 cmhigh, the bottom face is made of 16 mesh metallic wire), the inner faceon which butter was applied, and the container was set at the bottom ofa test chamber (bottom face: 46 cm×46 cm, height: 70 cm).

Each 1.5 ml of the oil solution of the compound of the present invention(1), (2), (3), (4) and (5) was sprayed using a spray gun at a pressureof 0.4 kg/cm² from 60 cm higher than the upper face of the container.Thirty seconds after the spraying, the container was pulled out from thechamber. Two minutes after spraying, the number of knocked-downcockroaches was counted and a knock-down ratio was determined (repeatedonce). A knocked-down ratio was calculated by the following equation.Knocked-down ratio(%)=(Number of knocked-down cockroaches/Number of testcockroaches)×100The results (2 minutes after spraying) are shown in Table 5.

TABLE 5 Knock-down ratio (%) Test compound 2 minutes after sprayingcompound of the present 100 invention (1) compound of the present 100invention (2) compound of the present 100 invention (3) compound of thepresent 100 invention (4) compound of the present 90 invention (5)

INDUSTRIAL APPLICABILITY

The compound of the present invention has an excellent pest controleffect and is therefore useful as an active ingredient of a pest controlagent.

The invention claimed is:
 1. An ester compound represented by formula(1):

wherein R¹ represents C₁-C₄ alkyl.
 2. The ester compound according toclaim 1, wherein a relative configuration of the substituent at the1-position of the cyclopropane ring and the substituent at the3-position of the cyclopropane ring is a trans configuration in formula(1).
 3. The ester compound according to claim 1, wherein an absoluteconfiguration of the 1-position of the cyclopropane ring is an Rconfiguration in formula (1).
 4. The ester compound according to claim1, wherein an absolute configuration of the 1-position of thecyclopropane ring is an R configuration, and a relative configuration ofthe substituent at the 1-position of the cyclopropane ring and thesubstituent at the 3-position of the cyclopropane ring is a transconfiguration in formula (1).
 5. The ester compound according to claim1, wherein a double bond of the substituent at the 3-position of thecyclopropane ring is in the E configuration or a mixture of Econfiguration and Z configuration, and the proportion of the Econfiguration is 50% or more in formula (1).
 6. The ester compoundaccording to claim 1, a double bond of the substituent at the 3-positionof the cyclopropane ring is in the E configuration in formula (1). 7.The ester compound according to claim 1, wherein R¹ is methyl in formula(1).
 8. The ester compound according to claim 1, wherein R¹ is ethyl informula (1).
 9. The ester compound according to claim 5, wherein R¹ ismethyl in formula (1).
 10. The ester compound according to claim 5,wherein R¹ is ethyl in formula (1).
 11. The ester compound according toclaim 6, wherein R¹ is methyl in formula (1).
 12. The ester compoundaccording to claim 6, wherein R¹ is ethyl in formula (1).
 13. A pestcontrol agent comprising the ester compound according to claim 1 and aninert carrier.
 14. A method of controlling pests, which comprises a stepof applying an effective amount of the ester compound according to claim1 to pests or a place where pests habitat.
 15. A method of controllingpests, which comprises the step of applying an effective amount of theester compound according to claim 1 to cockroaches or a place wherecockroaches inhabit.
 16. The method of controlling pests according toclaim 15, wherein the cockroach is American cockroach.
 17. The method ofcontrolling pests according to claim 15, wherein the cockroach is Germancockroach.
 18. A method of controlling pests, which comprises a step ofspraying an effective amount of the ester compound according to claim 1to cockroaches or a place where cockroaches inhabit.
 19. The method ofcontrolling pests according to claim 18, wherein the cockroach isAmerican cockroach.
 20. The method of controlling pests according toclaim 18, wherein the cockroach is German cockroach.